Process for the manufacture of a hydrocarbon solvent



July 22, 1952 c. MORRIS ET Al.

PROCESS FOR THE MNUF'ACTURE OF' A HYDROCRBONv SOLVENT Filed Dec. 29, 1945 1N V EN TOR LLOYD C. MORRIS FREDRICK M. SMITH www5 .FIOD

. offaroma-tic constituents have desirableeffects in ,Patented July 22, 1952 UNITED s'rA'rEsl PATENT oFFIcEaf-f PROCESS FOR THE MANUFACTURE'OEA.' HYDROCARBON SOLYENT.v

Lloyd C. Morris-l and VFredrick Smitl1,1Bartles-1j vil1e0kla., assignors to "Phillipsv 'Petroleum' Companma vcorporation of Delaware Application-.December 29, 1945, SerialfNo. 838,410.1y

3 Claims. (Cl. 26o-671)' higlifboiling :solvent -naphthas. 'In' a preferredvspeciiicembodiment'fit-relatesto a process for the treatmentfof a cracked lnaphtha fraction comprisingaromaticA Wand fnaphthenic constituents in admixture With'highsboiling olens, vand boi'lingiin 1 a `range between' about 250 and about 500i.:F.;"-Whereinfolensin-said fraction are rel movedein"an;.alkylation stepto provide residual naphthasin theesame-boilingrange characterizedv by .'ahighi concentrationof cyclic constituents and. possessingfpreferred solventproperties.

In.;the manufacture-'of .gasolines and motorl fuelszitahas 4`beerrfound .that high-concentrations e increasingv octane ratingrandvarious processes have :been hdeveloped for .the production of high aromaticityinwsuch fuels.- -In.r some .instances highj-boilingnaphthas or ,gas-:oils aresubjected` to controlled temperature catalytic. cracking treatment4 underv conditions '-for the production. oit-a motor fuelcf substantial aromatic content'.

YNa-phthas havingv ahigh degree of aromaticity While these long-.chain olensconf culties.-such Aas oxidation.. reactions .with 'the solutefandlthe. like.

InzA recent Y,years there vhasbeen Va constantly increasingdemandfor hydrocarbonsolvents,A not` 'onlygforconventionaluses suchas in dry `clean.v

ing. the vmanufacture of paints, vvarnishe`s, Water.- proong agents, etc.. but also for newly developed productaand processes involving specialized-.requirements not met-by ordinary commerciallyf` avai1ablefsolvent .materials...For 1.-.example, theW production*A of. insect rrepellents `and insecticides.

hascreatedz'a need for an organicfsolvent which isfcapablef offcarryingin solution a relatively. larger'concentration fof'. active substance and. is.

able odor,:.nontoxic to man zand. animals, .has ,a high flash point, and is relativelynon-volatile.i

Thefsolvent value of `a hydrocarbon fraction isj'finziaxgeneral "sense, Adetermined by its. content of zcycliczconstituents. That is, for example, a paratlinic material such as n-heptane may be. said-'to have a relatively'low solvent value in comparison-with -a cyclic material suchas benzeneor oyclohexane, While .-.a mixture, say... of r benzene .45 '.ahthesisame, time freeirom color andobjectionwithvnrheptanalwll havean. intermediate. solven value .depending :upon `the .relativeproportionjj its constituents... We have now found `that JayV contacting a frac-5.. tion of catalytically crackedv gas oil boiling in the approximate range 250 to r500 F; and comprising.; aromatic .and napl'ithenic constituents in admix"l ture withlong. chain. o1e1ns with va lower boiling. aromatic substance under alkylating conditions; said` oleilns are converted Yto *high-#boiling alkyl' benzenes and residual 4naplithas 'of high solvent power canbe obtained. An object of our-invention1is tofdecrease-thee olen. contentof a hydrocarbon,material'jcon- .taining olens asminorconstituents? ff Anotherl object g ofY our--im'fentionis` to"V produce-fa desirable'hydrocarbon solvent.

A further object of our-invention-is toflftratfd remove substantially -all "of the fole'n' hydrocarz-fwbons. y Still a further object-of the invention is to re-f-fA move oleiinV hydrocarbons from" admixturewitl 11 aromatic andnaphthene hydroc'arbon'sf Other ob'jectsand advantages of our inventit'n'ifhY will become a'1':iparent',v-r tfo one'skilled vinthelair from the"accompanyingdescriptionand discus l sion;- 1 Ina more general embodiment the' process of?A the Apresent`Y invention comprises the steps :-i (1') preparation' ofa feed stock.. comprising -1aromatic'i rf and v napht-henic constituents V -in vadm iid'lure I vvit long-'chainAand branched-chain'olens by frac naphtha or gasoilto produce a cut b tailingirithev approximate'rangeZO to'500 F." 2) contactin" said fractionv with a molar excess Vof-a lowerfboil ing-aromatic substance'under alkylating' condi tionswhe'reby"substantiallyfall{olens I'zre'seni'fare'fl converterto m'ghboinng; vaikyi pen'zeifes ,(3) stripping g out unreacted low-boiling Ljaroma,'tiz's substancefon ,recyclingitothe ;reaction;j(4 'fxja'c tionation of the effluent to ,i separate naph -boiling in the same- 'range jasthe` 'i'eed" stock having preferredsolvent:value]' The feed stockjemployedjcomprisesa relativel highlpercentag'e, Aof J aromatic, naphtheniian condensediring cyclicconstituents;gnerallygsub 'stantially'lJmore .than 50`per "cent, by volume; Jn'f' admixture Withja 'substantial per cent1by .volu ir`rejA of olen's ranging in carbon content,iromabout vseven to about sixteen carbon atonisito'thefmolie-lV cule and lesser. amounts'of Vparaiflnic hydrocar'-, y bons and. may .beprepared by .catalytijc'crackinglg of high-boiling naphthas or gas oils, for example, by a Cycloversion process, and fractionating the effluent to separate a cut having an initial boiling point not lower than about 250 F. and an end point not greater than about 500 F.

The aromatic substance employed may comprise benzene, ,benzene homologues, or mixturesn thereof, said aromatic substance being so chosen that its boiling point is in a range lower than that of the feed stock by an amount sumciently great to permit stripping out unreacted portions t subsequent to the alkylation operation. The pro#` portion of aromatic substance employed is in sub-.-

stantial molar excess of the olenic content or the feed stock, generally in a ratio of from about 5:1to 15:1. n 1 'Y a' The alkylation catalyst employed may be `one of a variety of alkylating catalysts. erally prefer to use a catalyst comprising a liquidrand moreV particularly complexesV or adi dition compounds .of 'boron uoride'zwith water,

We genexample, a fraction boiling between about 400 and 450 F. provides a superior solvent for insect repellents and insecticides since it embodies substantially all the specific properties required Yfor the preparation of highly eiective solutions .of these recently developed products which are non-staining, free from objectionable odor, and of excellent lasting quality.

A fraction boiling between about 300 and 425 F. provides Stoddard solvent of superior grade, suitable for employment in the dry-cleaning in# dustry. Painters and varnish-makers naphtha is obtained in the cut boiling between about 250 and 425 F. .By suitable adjustment ofthe boiling range solvents applicable to many other uses are available.

A further advantage in the present process ...lies in the production of valuable alkyl benzenes phosphoric-acid; or aqueous hydrogen'flurogriclegxr although Aother types and materials, ,such as sul.;

furie Vacidfvarious .sulfonic .'acids,.hydrofluoric acid, and. solid catalystssuch as an aluminum halide, alone or as a pari-of an organi'cjor in'- organic .complex solid phosphoric, acid, *silica-1 alumina, etc.;l are -not excluded. Also lthe" employment of. starting materials of. a suitable nature produced by othermethodsythanthe aforementioned catalytic Y cracking .process is withnthe scopeof ourA invention. Y .A mostv significant advantage of our preferred process lies inthe jsuperior'solvent value of the.'k naphtha -produced.j Aromatic, naphtheni and Y condensedV ring cyclic constituents fromthevieecl stock; jare concentrated in Y the residual naphtha whenolefins are removed in the alkylation step.

The relatively higliv index ofrefraction -and Vthe l high density and lowv aniline number :of the product indicate aromaticity substantially above that of ordinary ommercially'available hydro.`

carbonfsolvents boiling inthe same range:` TheV superior solventv propertiesqof our product are further indicated byvv the; unusually high kauributanoljand dimethyl y. sulfate values',A the low bromine number' and satisfactory Yflash point.

Other desirable properties vare its excellent color, low odor, and substantialfreedom fromv toxicity.

In connection with :this invention the boilingv ran'geyinitial'boilnigA point, Yend* point,Y and the Y like'are to fbe vdetermined by the rwell-known A.7^ S:A T: M; procedures. I The kauri-butanol values arefdeterminedV substantially Y as Y described by Gardner in Physical and Chemical Examinatijonffof,Y Paints, *'Varnishes, Lacquers and Colors,frpublished by the; National Paint, Var-'I nish and Lacquer Association.' 'A highkauributanol; .;value indica-teef a 'highf solvent power.- The. dimethyl sulfate -evalues Aare determined' substantially .as described bythe sameauthor inthe s ame publication, andgive. directly the percentage of. aromatic. constituents andlun-v saturated'aliphaticv hydrocarbons of .the olefin series. 'I'he value should b'efhigh .f'orajgood lacquer solvent.: although, Aas discussed herein,r

.oleflnf.contentshould be low, Vas indicated by a 1ow-.brominelnumber.By the .properpracf` tice of.` our vinventionit .is'y possible to reducethe olefin`- content sothatA the bromin'e number'v isV notV greater than .1.0, andvit will'usually be some.- what lessthan this .value./ L

.of the process through pipe I5.

nSince-*the totalproduct from our process boils i in 'a lrelatively broad. range, selected Vflactions may be separated for various specific uses. For

as byeproducts from the alkylation step. Other advantages inherent in Vthe invention will be evident from the'description of the accompany-t ing ,sketchY which 'illustrates in diagranimatie".v form yone type of apparatus in'which the objects" of our invention can be accomplished.

Referring now to the drawing, a high-boiling'r naphtha or gas oil is 'passed through pipe l0 to catalytic cracking unit Il. A typical charge stock is a gas oil separated from aV Mid-Continent [crude having an' initial boiling* pointl of w about 250 to 300 a 90v per cent distillation;v point of about '700 F., and a gravity of about= 36 A. P. I. Catalytic cracking unit Il will conv tain one or more catalytic reaction chambers t iilled withl a catalyst suchgas'granular bauxite;- The charge is'heated to a temperautre between. v aboutY y350 and A1050A FI-and lisA-fthen passed through the catalyst'bed'at aY-p'ressure between about 70. andrabout 100 pounds per square inch kgage. The now rate oi the gas oil'will be between about 5 kand about 10`barrels of oil per ton of catalyst per hour.' lf desired steam or some .other gaseous diluent'inay be added to the chargethrough pipe i2, VYIf 'steam is used'a suit Yable flowrate will be between about 0.2 and Aabout 0.5 pound' per pound` ci"j gasA oil'per -liourV` and thebed of catalyst canl be usedyfor between about 3 and about 8 hours before sufcient carbon has accumulated on it Yto requirev stoppingy of Vthe iiow o reactants and:` regeneration of the catalyst bed. Reaction effluents pass through l pipe i3 to separating means lf3, which will comi prise suitable heat exchangers,A fractionating" columns, pumps, heaters, coolers, accumulatore, and the like as can be supplied in any particular instance by one skilled in the art. conversion substantial quantities ofY hydrocarbon products boiling in the'fgasoline range will be produced and can be recovered as a'prod'uct gaseousconstituents will` also be produced and' can be remoyed through pipefl. Such products will `cemprise substantial amunts oi olen l'iy-I drocarbons which can be used as desired, for. example, for alkylation by freaction withiso.

butane to produce additional /hydrocarbon ina-cA in a gasoline product. Any undesired heavy products can -be terials suitable giorV inclusion discharged through pipe Il. A hydrocarbon fraction boiling preferably above 250 F. 'and not higher thanabout 500 F..

is removed through pipey i8 as a raw material for the `production of a hydrocarbon solvent. This fraction will generally contain over fper YcentmolfV aromatic and naphthene hydrocarbons. Itwill contain a smaller but substantial quantityv In such' a` Normally .amaca catalyst underYV alkylation-Y-conditions@whichf-nclude#` a reaction 'time--vsu'cientfor substantial-ly complete-reactionofw-'the'oleiins inthev--charge stock.: A suitablereaction! temperature between about f50 :a1'1d-150F'-v F51 and suicientapressure to.. maintenir-ii the reactantsin l liquid --phase tis also generally used I Effluentsf ot- Athe alkylationi are passed vthrough pipe 2| to separating means22 -l whichA willalsov include suitable separation and fractionalY distillationequipment. Unreacted benzene can beseparatedand returned to alkylation 19 through *pipezr Heavy-hydrocarbons comprisingrprimarilyrhigheboiling :aromatic alkyl hydrocarbons' produced in the;.' allr.ylation.step` are separatedv -fthroughapipe- Y-Zd. In lmany instances these'alkyl aromatic hydrocarbons can bereadily ,sulfonated and the` resulting sulfonic acids have excellentv detergent propertes..- An olefin-free hydrocarbon -solvent which willhave a 'high` content of aromatic andk naphthene Y hydrocarbons lis recovered -as a product of the-process-through-pipe 23.v

As willf'berl readilyl appreciated-leach `of *the reaction units has beenshown `l`only diagrammaticallyf@ Each such unit-involves processes y which vare not: noveltor the- -present invention per `se land operate-under 4conditionsV and inequipf ment whichl 'can' be vreadily*determined andl sup-` plied by one skilledin the art; Y Such equipment includes catalyticicrackingreactors; :heating furnaces, waste heat boilers, ,means forV supplying air [for catalyst regeneration,. means for supply.

ingsteatmgor combustion gas orY theglike,' as :dil-

uent material ,both for the catalytic cracking operation. when such is desired and vfor the cata,

alyst regeneration step.' As'previously .mentioned separating means I4 and 22'will each comprise suitable fractional distillation equipment and associated heaters, coolers, pumps, and the like. Alkylation unit I9 Will include alkylation reactors, catalyst separators, coolng equipment, pumps, and the like.

We Vhave found that a particularly desirable solvent is ultimately obtained through pipe 23 when the catalytic cracking carried out in cracking unit II is similar to that known to the art as Cycloversion A more detailed discussion of the operation has been discussed by Schulze and Helmers in the Oil and Gas Journal for April 13, 1944. However, we have also determined that desirable solvent fractions can be produced by the practice of our invention from high-boiling hydrocarbon fractions obtained from efliuents of any of the well-known commercial catalytic cracking operations such as those employing a so-called fluid cracking catalyst, the T. C. C. catalytic cracking process, and similar processes. containing cyclic hydrocarbons and smaller quantities of olefin hydrocarbons is available from any other source it may likewise be employed as a charge for the process of our invention.

Example The followingY is an example of our invention.

If a charge stock` A virgin gas oiL obtained; from: a .TeXasfPanhandle'f' crude oil was .icatalytically:cracked-in .a- .fCycloj-z.

argravity off36;5^'"A. P I-f It Twas cracked bybeing passed. through a fixed-bed ofgranular.l .bauxite .z

atta rate' of1.'7.6: barrels Vperyton of :catalystv per noun'. in :admixturei with .steam passed: at: a. rate of 40 .pounds vper barrel of'gas, oil.. .The temperaturenat the inletofthe catalyst chamber-twas' 101,5 '.F. fand at theoutlet was. 940".v F., and :the 1 pressureatiatheginletwas 95 pounds per. square?` inchlgagef: Theunitiwaszoperated for periods of.` six.: hours betweeikcatalyst regenerations.- Ef..i

`fluents..of.tl1e:pro1:.ess were.; subjected to fractional,

distillation; and: there;v was separated;Y av cut; boil? inghingthe; approximate: range 'off/10.0 :to ..45 O F. This. material hadthe properties 1shownincolumn.l r. A of the following;table;andl `hadfthe following..

A sample of this fraction weighing 17,510 grams Wasl mixed with 17,'590grams 'ofv benzene-"and 1600 cc."of catalyst prepared by saturating'hydro "iluoric'v acid with boron uoride.- Thev mixture wasv maintainedat a temperature",-between'-120`4 and" V130" EierY one hounwithY mechanicalrstir-n ring; The 'catalyst' was separated byngravityrthel eluentjwashedto remove traces of catalyst-dried 'over'solid sodium `hydroxide andunreactedV bene` zene' removedfby distillation'. The productl was then fractionated to-I yield A12,910gramsY vof oil boiling in the rangefof 400v to y4:50 F. `lf'roperties' of the oil are shown in column B in 'thefollowing table. For ypurposes of comparisonfsimilar properties-of a commercial hydrocarbon" solventm are shown in column C and of a typicalY Mid-ContiH nent kerosene in column D. All values were" obtained oniractions boiling in the 400 to450 range. 'o n Y A QB 'Ic p Gravity, A. Pfl. 60 F 39. 2 40. 5 46.9 Y Index of Reraction 68 F. 42 2 (20 C.) 1. 4612 1. 460 1. 441 1. 421 Bromlne Number 18. 0. 6 3.0 (2) Anllme Point, C. ("F.) 43.5 49. 7) 73.6 67.7

' 121. 5 164. 5 153. 9 Kami-Butanol Value, cc.. 42. 3 43.0 28. 1) 31% Solvent power, per cent 1 17,0 15,4 2.0 6. Dimethyl sulfate va1ue. 16. 0 3. 0 4. Saybolt color +26 +13 'lotal Sulfur 0. 013 0. 044 0. 024 Flash Point, F 170 170 181 7 l Based on benzene as and n-heptaue vas zero. 7 Less than 1.

It will be appreciated that various modifications of our invention can be practiced without departing from the scope and spirit of the disclosure and teachings, and without departing from the scope of the claims.

We claim:

1. An improved'process for the production of an olefin-free, aromatic hydrocarbon fraction, which comprises subjecting a gas oil petroleum fraction to catalytic cracking at an elevated temperature to produce a hydrocarbon material boiling between about 250 to about 500 F. containing at least 50 per cent by volume of aromatic and naphthene hydrocarbons and the remainder primarily olen and parain hydrocarbons, said olen hydrocarbons being 10 to 30 per cent by that theratio of said aromatic to the olefin will be in the range :1 to 15:1, subjecting the resulting liquidmixture to theaction of an alkylation catalyst under alkylationconditions for a time suicient to react by alkylation substantially the entire olefin content of said mixture, and recoveringfrcm effluents of said alkylation an olenfree aromatic hydrocarbon material with an initial boiling point not less lthan about 250* F.

and an end point not greater than about 500 F.

Y containing the first said paramn, naphthene, andl aromatic hydrocarbons and also being free from reaction products of said alkylation.

2. An improved processiorremoving olens from ahydrocarbon material boiling above 250 F. and containing substantially more than 5i) perV centby volume of aromatic and naphthene hydrocarbons and also i0 to 30V percent by volume of olefins as undesired constituents, which comprises adding to said material a lower-boiling aromatic hydrocarbon in an amount greater than that rnolec'ula'rly equivalent to the olen content of saidV hydrocarbon materialsuch that theratio of said aromatic to the olefin will be inthe range 5:1 tov 15:1, subjecting the resulting liquid mixture to the action of an alkylation catalyst comprising hydrofiuoric. acid saturated with boron triiluoride ,under alkylation conditions for. a time sufficient to effectsubstantially complete 'reaction of said oleiins, an'd'recovering from eiiiuents of Ysaid alkylation a hydrocarbon .fraction boiling above 250 YF. having a bromine number less thanv 1.5 and containing substantially all of the arcinatic and naphthene hydrocarbons present in said original hydrocarbon material and being free from reaction products of said alkylaticn.

3. An improved process for treating a hydro- 8'; boiling within the saine `range and suiciently freefrom olefin hydrocarbons as to have a bromine number not greater `than 1.0, which comprises adding benzene to said hydrocarbon mix-.vA ture in an amount at least iive timesV the molecular equivalent of the olens in said mixturasulzv-v jectingthe resulting'liquid mixture to the action of an Valkylation catalyst a1; a reaction temperature not greater than F. while under a p ressure sufficient to maintain the reactantsinliquid phase for a time sufficient to effect complete reaction of the olefin content of said hydrocarbon Y mixture by alkylation, and recovering from eilluf ents of said alkylation va hydrocarbon mixture boiling between 400 and-450 F. and having a bromine number not greater than 1.0 as a product; of the process, said product containing said parafn, naphthene and aromatic hydrocarbons and being Vfree from reaction products of said alkylation.

Y LLOYD C. MORRIS.

FREDRICK M. SMITH.

REFERENCES CITED The following references are of record in th le of this patent:

UNITED STATES vPA'inNrs 'Date Y Number Name 1,878,963 Michel sepnzo, 1932l 1,933,434 *Y Hofmann et .ral.'* Oct. 3l, 1933 2,009,103 Egioir 1 July 23, 1935 2,035,889 Ipatieff Mar. 3l, 1936' 2,187,034 Ipatel et al. Jan. V16, 1940 2,269,279 DOuville et ai] Oct. 21, y1941 2,324,784 Lieber July 20, 1943 2,343,870 Kaplan Mar, 14,1944

2,379,368 Matuszak June 25, 1945V 2,396,682 Carmody i- Mar. 19, 1946.v 2,399,662 Burk et al.l p v May 7, 1946 2,415,272 Benedict el', al Feb. 4:, 1947V O'IHERy REFERENCES Flowers et al.: Chemical Processes for Re-reiningand Decolorizing Dry Cleaners Solvent by Continuous vAutomatic Methods.v Pub. by De Laval Separator Co., Experimental Department, Poughkeepsie, New York. Report No. 462. February 20, 192,7. Page 5 (l page). 8-142. 

1. AN IMPROVED PROCESS FOR THE PRODUCTION OF AN OLEFIN-FREE, AROMATIC HYDROCARBON FRACTION, WHICH COMPRISES SUBJECTING A GAS OIL PETROLEUM FRACTION TO CATALYTIC CRACKING AT AN ELEVATED TEMPERATURE TO PRODUCE A HYDROCARBON MATERIAL BOILING BETWEEN ABOUT 250 TO ABOUT 500* F. CONTAINING AT LEAST 50 PER CENT BY VOLUME OF AROMATIC AND NAPHTHENE HYDROCARBONS AND THE REMAINDER PRIMARILY OLEFIN AND PARAFFIN HYDROCARBONS, SAID OLEFIN HYDROCARBONS BEING 10 TO 30 PER CENT BY VOLUME OF SAID HYDROCARBON MATERIAL, SEPARATING SUCH A HYDROCARBON MATERIAL FROM EFFLUENTS OF SAID CATALYTIC CRACKING, ADDING TO SAID MATERIAL A LOWER-BOILING AROMATIC HYDROCARBON IN AN AMOUNT IN EXCESS OF THAT MOLECULARLY EQUIVALENT TO THE OLEFIN CONTENT OF SAID HYDROCARBON MATERIAL SUCH THAT THE RATIO OF SAID AROMATIC TO THE OLEFIN WILL BE IN THE RANGE OF 5:1 TO 15:1, SUBJECTING THE RESULTING LIQUID MIXTURE TO THE ACTION OF AN ALKYLATION CATALYST UNDER ALKYLATION CONDITIONS FOR A TIME SUFFICIENT TO REACT BY ALKYLATION SUBSTANTIALLY THE ENTIRE OLEFIN CONTENT OF SAID MIXTURE, AND RECOVERING FROM EFFLUENTS OF SAID ALKYLATION AN OLEFINFREE AROMATIC HYDROCARBON MATERIAL WITH AN INITIAL BOILING POINT NOT LESS THAN ABOUT 250* F. AND AN END POINT NOT GREATER THAN ABOUT 500* F. CONTAINING THE FIRST SAID PARAFFIN, NAPHTHENE, AND AROMATIC HYDROCARBONS AND ALSO BEING FREE FROM REACTION PRODUCTS OF SAID ALKYLATION. 